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Improving the predictive quality of time‐dependent density functional theory calculations of the X‐ray emission spectroscopy of organic molecules

Fouda, Adam A. E.; Besley, Nicholas A.

Authors

Adam A. E. Fouda

Nicholas A. Besley



Abstract

The simulation of x-ray emission spectra of organic molecules using time-dependent density functional theory (TDDFT) is explored. TDDFT calculations using standard hybrid exchange-correlation functionals in conjunction with large basis sets can predict accurate X-ray emission spectra provided an energy shift is applied to align the spectra with experiment. The relaxation of the orbitals in the intermediate state is an important factor, and neglect of this relaxation leads to considerably poorer predicted spectra. A short-range corrected functional is found to give emission energies that required a relatively small energy shift to align with experiment. However, increasing the amount of Hartree-Fock exchange in this functional to remove the need for any energy shift led to a deterioration in the quality of the calculated spectral profile. To predict accurate spectra without reference to experimental measurements, we use the CAM-B3LYP functional with the energy scale determined with reference to a ∆self-consistent field (SCF) calculation for the highest energy emission transition.

Journal Article Type Article
Publication Date Apr 30, 2020
Journal Journal of Computational Chemistry
Print ISSN 0192-8651
Electronic ISSN 1096-987X
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 41
Issue 11
Pages 1081-1090
APA6 Citation Fouda, A. A. E., & Besley, N. A. (2020). Improving the predictive quality of time‐dependent density functional theory calculations of the X‐ray emission spectroscopy of organic molecules. Journal of Computational Chemistry, 41(11), 1081-1090. https://doi.org/10.1002/jcc.26153
DOI https://doi.org/10.1002/jcc.26153
Keywords General Chemistry; Computational Mathematics
Publisher URL https://onlinelibrary.wiley.com/doi/full/10.1002/jcc.26153
Additional Information Received: 2019-10-15; Accepted: 2020-01-08; Published: 2020-01-22

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